Process for the finishing of textile



v or two ethylene linkages.

United States Patent 3,123,496 PROCESS FOR THE FINISHING 0F TEXTILE MATERIALS Paiil Schlack, Leitershofen, near Augsburg, Gerhard Lohaiis, Bad Soden, T-aunus, Hans Sommer, Hofheim, Taunus, and Gerold Koch, Frankfurt am Main, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Briining, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Filed Oct. 5, 1960, Ser. No. 60,584 Claims priority, application Germany Oct. 9, 1959 5 Claims. (Cl. 117-161) It is known to use solutions, dispersions, or emulsions of polymers obtained from monomers that contain vinyl groups in order to obtain special effects on two-dimensional textile structures or on yarns and filaments The finishes produced with these known processes have a certain fastness to washing which, however, is in most cases unsatisfactory for practical requirements.

Now, we have found that finishes of various kinds which exhibit an essentially better fastness to washing can be produced on textile material with solutions, dispersions, or emulsions of vinyl polymers obtained by copolymerization of monomers that contain vinyl groups and acyl urethanes that contain a polymerizable double linkage. The copolymerization is effected in accordance with known methods in aqueous solutions, emulsions, or suspensions at room temperature or preferably at an elevated temperature up to 100 C. When operating in this way there are usually used, in addition to emulsifiers and protective colloids, activators that form radicals, for instance hydrogen peroxide, alkali metal persulfates and the like.

The proportion of acyl urethanes in the copolymer used in the present invention can vary within wide limits. In general, there are used quantities of about 0.5 to 90 parts by weight, preferably about 2 to 20 parts by weight, of acyl urethanes per 100 parts by weight of copolymer.

As acyl urethanes there are used compounds of the general formula in which R-CO represents the radical of a monobasic or polybasic carboxylic acid which is unsaturated in one or several positions and which, in the case of a polybasic carboxylic acid, may additionally be esterified with aliphatic alcohols of low molecular weight containing 1-6 carbon atoms, or the carboxyl groups of which may be substituted by the carbamic acid ester radical X stands for oxygen or sulfur, and R stands for a low molecular weight alkyl, cycloalkyl, aryl or aralkyl radical which, if desired, may be substituted, in particular by alkoxy radicals. As the group RCO, there enters into consideration preferably the radical of a mono or dibasic carboxylic acid containing up to 6 carbon atoms and one As such, there are mentioned by way of example: acrylic acid,methacrylic acid, crotonic acid, itaconic acid,-citraconic acid, mesaconic acid, muconic acid, maleic acid, aconitic acid, etc. Mixtures of the acyl-urethanes may also be used.

Particularly good results are obtained with acylurethanes of the above-indicated formula, when compounds are used in which R means a cycloalkyl or an alkyl radical containing up to 6 carbon atoms, which radical maybe substituted by methoxy or ethoxy radicals, for example the methyl, ethyl, isopropyl, butyl, isobutyl, n-hexyl, isohexyl, or also the ,B-methoxyethyl radical.

As acyl urethanes there are mentioned:

N-acryloyl carbamic acid-butyl ester, N-acryloyl carbamic acid isopropyl ester,

"ice

N-acryloyl carbamic acid-,B-methoxyethyl ester, N-crotonyl carbamic acid-B-methoxyethyl ester, and the compounds for the formulae HOC O O C4110 and HCC O O CaH- Hoo ONH-C 0 0 04m As compounds that contain vinyl groups and that may be used' for the copolymerization with the unsaturated acyl urethanes, there are suitable compounds which con tain one or several polymerizable ethylene double linkages as for example: the unsaturated alcohol esters more particularly the allyl, methallyl, crotyl, vinyl, propargyl, etc., esters of saturated and unsaturated, aliphatic and aromatic, monobasic and polybasic acids such as, for example, acetic, propionic, butyric, acrylic and alpha-substituted acrylic (including alkacrylic, e.g. methacrylic etc.,) crotonic, malonic, adipic, maleic, citraconic, itaconic, acetylene dicarboxylic, phthalic, etc., acids; the saturated monohydric alcohol esters, e.g. the methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, amyl, etc., esters of unsaturated aliphatic mono-basic acids and polybasic acids; vinyl cyclic compounds (including monovinyl aromatic hydrocarbons), e.g. styrene, o-, mand p-chlorostyrenes, o-, mand pmethylstyrenes, the various poly-substituted styrenes such, for example, as vinyl cyclohexane, vinyl pyridine, divinyl benzene, allyl benzene, the various allyl cyanostyrenes, the various alpha-substituted styrenes and alphasubstituted ring-substituted styrenes, e.g., alpha-methyl styrene, alpha-methyl-para-methyl styrene, etc.; unsaturated ethers, e.g., ethylvinyl ether, diallyl ether, ethyl methallyl ether, etc.; unsaturated amides, e.g., acrylamide, and N-substituted acrylamides, e.g. N-methylol acrylamide, N-methyl acrylamide, etc.; unsaturated ketones, e.g. methyl vinyl ketone, methyl allyl ketone, etc.; butadienes, e.g. 1,3-butadiene, Z-chlorobutadiene, etc.; unsaturated polyhydric alcohol (e.g., butenediol, etc.); esters of saturated and unsaturated, aliphatic and aromatic, monobasic aud polybasic acids. Other examples of monomers that may be copolymerized with the acyl urethanes are the vinyl halides, more particularly vinyl chloride, and the various vinylidene compounds, including the vinylidene halides, e.g., vinylidene chloride.

The vinyl compounds may be copolymerized in the form of solution, bulk, emulsion or dispersion polymers, individually or in admixture with the acyl urethanes, according to a mechanism which uses for the polymerization either the relations between the radicals or ionic relations.

The following monomers that contain vinyl groups can be used with special advantage: the vinyl esters of ali phatic, low molecular carboxylic acids containing 1 to 4 carbon atoms, e.g. vinyl acetate and vinyl propionate, vinyl ethers of aliphatic low molecular alcohols containing l-6 Water or in inert organic solvents, for example in hydrocanbons such as benzine, benzene, toluene, or in liquid aliphatic chlorinated hydrocarbons of low molecular Weight, for example methylene chloride, carbon tetrachloride, trichlorethylene, ethylene chloride, tetrachlorethane, etc., or as aqueous dispersions or emulsions.

The textile material treated with these copolymers, if desired together with other known finishing or auxiliary agents, is then dried at an elevated temperature in order to be fixed. Temperatures higher than 60 C. to about 180 C. are suitable for this purpose, temperatures in the range of about 100-150 C., being preferred. The heating periods required may vary within Wide limits. Above all, they depend on the temperatures applied. At more elevated drying temperatures of about l30180 C., a heating period of only a few minutes is sufiicient in order to produce good wash-fast finishes. In practice, drying periods of about 1 to about 30 minutes are applied. These periods are approximate data only. In special cases the periods may be longer or shoiter.

With the copolymers of the present invention, there can be produced, for example, wash-fast filling or sizing finishes, embossing finishes, and finishes that are waterrepellent, oil-repellent, dirt-repellent or resistant to swelling and creasing.

The wash-fiastness of these finishes can often be increased by adding potential acid donators such as the ammonium salts of strong acids, for example ammonium chloride and ammonium nitrate, salts of bivalent metals with strong acids, for example magnesium chloride, zinc chloride or zinc nitrate. It is, however, also possible to apply the copolymers in an alkaline medium whereby very favorable results are likewise obtained.

The copolymers may also be used together with anionic, non-ionogenic or cationic agents that are conventionally used in the textile industry, for example, softening agents, emulsifying agents, pigments, hydrophobizing agents, insecticides, fungicides, or high quality finishes, for example anti-swelling and anti-creasing agents. As other known finishing agents that may be used simultaneously, there are mentioned by way of example: urea precondensates or melamine-formaldehyde precondensates, methylol compounds of cyclic urea derivatives, tri-azinones, and the like, further also precondensates of epoxide resins etc.

As textile materials that may be finished by the process of the present invention, there are mentioned, for example, yarns, filaments or two-dimensional textile structures such as fabrics or knit goods made from known fibrous materials, for example natural or regenerated cellulose fibers, natural or synthetic protein fibers, fully synthetic fibers such as polyamide, polyester, polyvinyl chloride, polyacrylonitrile fibers, furthermore glass and asbestos fibers. Other two-dimensional structures of fibrous nature, for example, paper, felt, etc. are likewise suitable.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto; the parts being by weight unless otherwise stated.

Example 1 315 parts of a solution of 5% strength of a polyvinyl alcohol having a K-value of 50 were introduced into a four-neck flask provided with thermometer, stirrer, reflux cooler, and a dropping funnel. In this solution was then dispersed to obtain an emulsion, with intensive stirring and at room temperature, a solution of 9 parts of N- acryloyl-carbamic acid-butyl ester in 300 parts of vinyl acetate. The pH was adjusted to 3 by means of formic acid, and 2.2 parts of hydrogen peroxide of 33% strength were added as activator. The mixture was heated to the boiling point of the azeotrope of vinyl acetate and water (66 C.) and after beginning of the polymerization the mixture was kept for 4 hours at this temperature. There was obtained a dispersion of polymeric material having a residual content of monomers of less than 0.7%.

A fabric from polyester fibers was immersed into a solution containing per liter 60 grams of the above-mentioned dispersion, then centrifuged to about 80% of residual moisture and dried at 90 C. After 3 washes in a house-hold washing machine withthe usual quantity of coarse detergent, the fabric had a residual stiffness in bend of 42% of its stiffness prior to the Washing. A sample of 4 fabric impregnated in the same manner, pre-dried at 60 C. and after-heated for 5 minutes at 140 C., exhibited after 3 washes a residual stiffness in bend of 78%.

Example 2 In the apparatus described in Example 1 was introduced the following polymerization mixture:

580 parts of water,

9 parts of the sodium salt of dodecylbenzenesulfonate,

12 parts of a solution of 25% strength of the sodium vinyl salt of sulfonic acid in water, and

3.5 parts of sodium acetate.

The pH was adjusted to 5-6 by means of acetic acid. This mixture was then heated on a water bath having 80 C. and a solution of 6 parts of N-acryloyl-carbamic acid-butyl ester in 54 parts of vinyl acetate is dropwise added during 15 minutes so as to obtain an emulsion, and then a solution of 3 parts of sodium persulfate in 50 parts of water is added dropwise. After the polymerization had started, a residual mixture of monomer consisting of 54 parts of N-acryloyl-carbamic acid-butyl ester and 480 parts of vinyl acetate was added within 1 hour and at a temperature of the reaction mixture of 80 C. The polymerization was terminated after a further 1 /2 hours. There was obtained a very fine dispersion which had a low viscosity.

A piece of cotton shirt poplin treated with lye was padded with a solution containing per liter 100 grams of this dispersion, squeezed on a padding mangle, and dried at C. After 10 washes at boiling temperatures, a residual stiffness in bend of 79% was still present, whereas a piece of cotton shirt poplin that had been padded with a solution containing per liter grams of the dispersion prepared according to the above prescription, however without addition of acyl urethane, exhibited after the same treatment and the same number of washes a residual stiffness in bend of 47% only.

When a heavy cotton fabric was coated with the described dispersion and dried at C., the coating obtained was transparent. The water-repellency of the coating produced with the dispersion containing acyl urethane was substantially better than that of a coating prepared with a pure polyvinyl acetate dispersion.

Example 3 Into the apparatus described in Example 1 was introduced a bath of the following composition:

495 parts of water and 25 parts of polyvinyl alcohol (K-value about 50).

The pH was adjusted to 3 by means of formic acid, and the whole was heated to 80 C.; into this mixture was dispersed so as to obtain an emulsion, a solution of 5 grams of N-crotonyl carbamic acid-[fl-methoxyethyl ester] in 45 grams of vinyl acetate. 1.1 parts of hydrogen peroxide of 30% strength were then added dropwise. After the polymerization had started, a solution of 45 parts of N-crotonyl-carbamic acid [ti-methoxyethyl ester] in 405 parts of vinyl acetate was added dropwise during 2 hours, while keeping the reaction temperature at 80 C. After a further 4 hours, the polymerization was terminated. There was obtained a dispersion having medium viscosity and a residual content of monomers of less than 1%.

A fabric of mercerized cotton shirt poplin was impregnated on a padding machine with a bath' containing per liter 100 grains of the above dispersion, and, in addition thereto, per liter 15 grams of dimethylol-ethylene urea and 10 grams of magnesium chloride; the fabric was then predried at 60 C. and after-heated for 5 minutes to 150 C. The crease recovery test in the moist state exhibited a crease angle of 213 and after 10 washes at boiling temperatures an angle of 252. Goods that were finished in a similar manner, but with a dispersion containing the same quantity of polyvinyl acetate, had an equal wet crease angle, but showed a wet crease angle of only 221 after ten washes at boiling temperatures.

Example 4 To a dyebath containing per liter 100 grams of the dispersion described in Example 2 there were added per liter grams of magnesium chloride. A fabric of viscose staple fibers was padded with this bath, dried at 100 C., and after-dried for 5 minutes at 140 C. For comparison, a similar fabric was finished in the same manner with a dispersion that contained an equal quantity of pure polyvinyl acetate together with magnesium chloride. In the wet state, the last-mentioned fabric exhibited a crease recovery of 77% of that of the first-mentioned fabric. After 10 washes at boiling temperatures, the crease recovery of the fabric that had been finished with the pure polyvinyl acetate dispersion was still 85% of that of the fabric finished with the dispersion containing acyl urethane.

ExampIeS' 20 parts of polyvinyl alcohol were dissolved in the manner described in Example 1 in 410 parts of water and then 40 parts of the following mixture of monomers were added while vigorously stirring for minutes:

245 parts of vinyl acetate, 125 parts of maleic acid dibutyl ester, parts of N-acryloyl-carbamic acid-butyl ester.

1.7 parts of hydrogen peroxide of 33% strength were then added dropwise to this mixture, and, after the polymerization had started, the rest of the above mixture of monomers was added in the course of 9 hours. There was obtained a very viscous, well-biushable dispersion.

The above dispersion was applied in a dilution of 60 grams/ liter to a staple fiber fabric and dried at 90 C. Another dispersion in which, however, the N-acryloylcarbamic acid-butyl ester had been replaced by the same quantity of vinyl acetate, was also applied to the staple fiber fabric. After 10 washes at boiling temperatures, the latter fabric had an impregnation coat amounting to 64% of that of the fabric coated with the dispersion containing acyl urethane.

Example 6 Into the apparatus described in Example 1 were introduced 450 parts of a solution of 0.1% strength of the ammonium salt of a copolymer of maleic acid and styrene. 15 parts of crotonic acid were added. In order to neutralize the crotonic acid, 35 parts of an unsaturated solution of sodium carbonate were added to the mixture which was then adjusted to a pH of 5. After having heated to 70 C., a solution of 15 parts of acryloyl-carbamic acid-butyl ester and 3 parts of benzoyl-peroxide in 270 parts of vinyl acetate were added with intensive stirring in the course of 4 hours. There were obtained clear glassy pearls which after washing and drying exhibited a residual monomer content of less than 0.3%.

The copolymer pearls prepared by the above method were dissolved in aqueous alcoholic ammonia to such an extent that 50 grams of solid substance were present per liter of solution which had a pH of 8.5. By the same process similar polymer pearls were also prepared without adding acyl urethane; these pearls were likewise dissolved in aqueous alcoholic ammonia at a pH of 8.5 so that the solution contained per liter 50 grams of solid substance. For comparison, cotton calico fabrics were treated with these solutions and dried at 100 C. After 3 washes with a commercial fine detergent at a temperature of 40 C., the fabric finished with the solution of copolymer containing acyl urethane still exhibited a good stiifness, whereas the other fabric which had been finished with the copolymer without acyl urethane was no longer stiff.

When instead of the copolymer obtained from vinyl acetate, crotonic acid and N-acryloyl-carbamic acid-butyl ester, a copolymer from vinyl acetate, maleic acid dibutyl ester, crotonic acid and N-acrylol-carbamic acid-butyl ester was used at a ratio of 220:15:15:45, and a cotton calico fabric was finished in the manner described, after 3 fine washes the stiffness of this fabric was still essentially better than that of a fabric finished with a copolymer from vinyl acetate, maleic acid dibutyl ester and crotonic acid at a ratio of 265 :15 :15.

Example 7 A dispersion was prepared as described in Example 2, but instead of N-acryloyl-carbamic acid-butyl ester the same quantity of N-acryloyl-carbamic acid-isopropyl ester was used as copolymer component.

A staple fiber fabric was made crease-proof by impregnating it with:

150 grams/liter of a commercial precondensate from 1 mol of urea and 2 mols of formaldehyde,

6 grams/liter of ammonium chloride, and

10 grams/liter of the above dispersion,

pre-drying the impregnated fabric at C. and condensing it for 4 minutes at C.;

' grams/liter of the urea-formaldehyde precondensate used under (a),

6 grams/liter of ammonium chloride, and

10 grams/liter of a'dispersion prepared as described in Example 2 but as homopolymer from vinyl acetate, finished as described under (a).

4 parts of acrylamide and 1 part of N-acryloyl-carbamic acid-[fi-methoxyethyl ester] were dissolved in 44 parts of water which had been freed from dissolved oxygen by boiling it out while simultaneously passing through nitrogen. 0.025 part of sodium persulfate dissolved in 0.5 part of air-free water was then added, the batch was heated to 40 C. and a solution of 0.0125 part of sodium metabisulfite in 0.5 part of air-free water was added dropwise, in the course of 1 hour and with stirring. A clear viscous copolymer solution formed.

A wool flannel was impregnated with an aqueous solution containing per liter 25 grams of the above-described copolymer and then dried at 90 C. The flannel so treated showed a firm, full hand even after several washes, whereas a finish produced with a solution in water containing per liter 25 grams of polyacrylamide completely disappeared after one wash.

We claim:

1. A process for the finishing of textile material, which comprises treating the textile material with a liquid medium comprising copolymers of (A) 0.5 up to 90 parts by weight of unsaturated acyl urethanes of the general formula wherein R represents a member selected from the group consisting of an alkyl radical containing 1 to 6 carbon atoms, an alkyl radical with up to 6 carbon atoms being substituted by an alkoxy radical with up to 2 carbon atoms, the cyclohexyl radical, an aryl radical of low molecular weight and an aralkyl radical of low molecular weight, X represents a memher selected from the group consisting of oxygen and sulfur, and R-CO- represents a member selected from the group consisting of a radical of a carboxylic acid containing up to 2 carboxyl groups, up to 2 ethylene linkages and up to 6 carbon atoms, a radical of a monoester of a dibasic carboxylic acid, said acid containing up to 2 ethylene linkages and up to 6 carbon atoms and said ester containing up to 6 carbon atoms in the alcohol portion thereof, and a radical of a monoacylurethane of a dibasic carboxylic acid, said acid containing up to 2 ethylene linkages and up to 6 carbon atoms, the urethane group having the formula NHCOXR', wherein R and X have the meanings given above, and

( B)from 99.5 to 10 parts by weight of monomers which contain vinyl groups and which are selected from the group consisting of styrene, a vinyl ester of carboxylic acids with up to 6 carbon atoms, a vinyl ether of alkanols with up to 6 carbon atoms, an unsaturated carboxylic acid containing up to 2 carboxyl groups up to 6 carbon atoms, an amide of said unsaturated carboxylic acid, and an ester of said unsaturated carboxylic acid containing up to 4 carbon atoms in the alcohol portion thereof, and drying the textile material so treated at elevated temperatures.

2. The process as claimed in claim 1, wherein 2-20 parts by weight of component (A) are copolymerized with 98 80' parts by weight of component (B).

3. The process as claimed in claim 1, wherein the copolymer is applied onto said textile material together with an acid donator.

4. The process as claimed in claim 1, wherein the copolymer is applied onto said textile material in an alkaline medium.

5. A textile material having thereon a dried coating of a copolymer of V (A) 0.5 up to 90 parts by weight of unsaturated acyl urethanes of the general formula wherein R represents a member selected from the group consisting of an alkyl radical containing 1 to 6 carbon atoms, an alkyl radical with up to 6 carbon atoms being substituted by an alkoxy radical with up to 2 carbon atoms, the cyclohexyl radical, an aryl radical of low molecular weight and an aralkyl radical of low molecular weight, X represents a member selected from the group consisting of oxygen and sulfur, and R-CO represents a member selected from the group consisting of a radical of a carboxylic acid containing up to 2 carboxyl groups, up to 2 ethylene linkages and up to 6 carbon atoms, a radical of a monoester of a dibasic carboxylic acid, said acid containing up to 6 carbon atoms in the alcohol portion thereof, and a radical of a monoacylurethane of a dibasic carboxylic acid, said acid containing up to 2 ethylene linkages and up to 6 carbon atoms, the urethane group having the formula wherein R and X have the meanings given above, and

References Cited in the file of this patent UNITED STATES PATENTS Cofiman Nov. 30, 1943 

1. A PROCESS FOR THE FINISHING OF TEXTILE MATERIAL, WHICH COMPRISES TREATING THE TEXTILE MATERIAL WITH A LIQUID MEDIUM CONTAINING COPOLYMERS OF (A) 0.5 UP TO 90 PARTS BY WEIGHT OF UNSATURATED ACYL URETHANES OF THE GENERAL FORMULA 